Compositions and methods for the deposition of silicon oxide films

ABSTRACT

Described herein are compositions and methods for forming silicon oxide films. In one aspect, the film is deposited from at least one silicon precursor compound, wherein the at least one silicon precursor compound is selected from the following Formulae A and B: 
                         
as defined herein.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority under 35 U.S.C. § 119(e)to U.S. provisional patent application No. 62/396,410, filed on Sep. 19,2016, U.S. provisional patent application No. 62/408,167, filed on Oct.14, 2016, and U.S. provisional patent application No. 62/417,619, filedon Nov. 4, 2016, the entireties of which are incorporated herein byreference.

BACKGROUND OF THE INVENTION

Described herein are compositions and methods for the formation ofsilicon and oxide containing films. More specifically, described hereinare compositions and methods for formation of stoichiometric ornon-stoichiometric silicon oxide films or material at one or moredeposition temperatures of about 300° C. or less or, more specifically,ranging from about 25° C. to about 300° C.

Atomic Layer Deposition (ALD) and Plasma Enhanced Atomic LayerDeposition (PEALD) are processes used to deposit conformal silicon oxidefilm at low temperatures (<500° C.). In both ALD and PEALD processes,the precursors and reactive gases (such as oxygen or ozone) areseparately pulsed in certain number of cycles to form a monolayer ofsilicon oxide at each cycle. However, silicon oxide deposited at lowtemperatures using these processes may contain levels of impurities suchas, without limitation, nitrogen (N) which may be detrimental in certainsemiconductor applications. To remedy this, one possible solution is toincrease the deposition temperature to 500° C. or greater. However, atthese higher temperatures, conventional precursors employed bysemi-conductor industries tend to self-react, thermally decompose, anddeposit in a chemical vapor deposition (CVD) mode rather than an ALDmode. The CVD mode deposition has reduced conformality compared to ALDdeposition, especially for high aspect ratio structures which are neededin many semiconductor applications. In addition, the CVD mode depositionhas less control of film or material thickness than the ALD modedeposition.

The reference article entitled “Some New Alkylaminosilanes”, Abel, E. W.et al., J. Chem. Soc., (1961), Vol. 26, pp. 1528-1530 describes thepreparation of various aminosilane compounds such as Me₃SiNHBu-iso,Me₃SiNHBu-sec, Me₃SiN(Pr-iso)₂, and Me₃SiN(Bu-sec)₂ wherein Me=methyl,Bu-sec=sec-butyl, and Pr-iso=isopropyl from the direct interaction oftrimethylchlorosilane (Me₃SiCl) and the appropriate amine.

The reference article entitled “SiO₂ Atomic Layer Deposition UsingTris(dimethylamino)silane and Hydrogen Peroxide Studied by in SituTransmission FTIR Spectroscopy”, Burton, B. B., et al., The Journal ofPhysical Chemistry (2009), Vol. 113, pp. 8249-57 describes the atomiclayer deposition (ALD) of silicon dioxide (SiO₂) using a variety ofsilicon precursors with H₂O₂ as the oxidant. The silicon precursors were(N,N-dimethylamino)trimethylsilane) (CH₃)₃SiN(CH₃)₂,vinyltrimethoxysilane CH₂CHSi(OCH₃)₃, trivinylmethoxysilane(CH₂CH)₃SiOCH₃, tetrakis(dimethylamino)silane Si(N(CH₃)₂)₄, andtris(dimethylamino)silane (TDMAS) SiH(N(CH₃)₂)₃. TDMAS was determined tobe the most effective of these precursors. However, additional studiesdetermined that SiH* surface species from TDMAS were difficult to removeusing only H₂O. Subsequent studies utilized TDMAS and H₂O₂ as theoxidant and explored SiO₂ ALD in the temperature range of 150-550° C.The exposures required for the TDMAS and H₂O₂ surface reactions to reachcompletion and were monitored using in situ FTIR spectroscopy. The FTIRvibrational spectra following the TDMAS exposures showed a loss ofabsorbance for O—H stretching vibrations and a gain of absorbance forC-Hx and Si—H stretching vibrations. The FTIR vibrational spectrafollowing the H₂O₂ exposures displayed a loss of absorbance for C-Hx andSi—H stretching vibrations and an increase of absorbance for the O—Hstretching vibrations. The SiH* surface species were completely removedonly at temperatures >450° C. The bulk vibrational modes of SiO₂ wereobserved between 1000-1250 cm⁻¹ and grew progressively with number ofTDMAS and H₂O₂ reaction cycles. Transmission electron microscopy (TEM)was performed after 50 TDMAS and H₂O₂ reaction cycles on ZrO₂nanoparticles at temperatures between 150-550° C. The film thicknessdetermined by TEM at each temperature was used to obtain the SiO₂ ALDgrowth rate. The growth per cycle varied from 0.8 Å/cycle at 150° C. to1.8 Å/cycle at 550° C. and was correlated with the removal of the SiH*surface species. SiO₂ ALD using TDMAS and H₂O₂ should be valuable forSiO₂ ALD at temperatures >450° C.

JP2010275602 and JP2010225663 disclose the use of a raw material to forma Si containing thin film such as, silicon oxide, by a chemical vapordeposition (CVD) process at a temperature range of from 300-500° C. Theraw material is an organic silicon compound, represented by formula: (a)HSi(CH₃)(R¹)(NR²R³), wherein, R¹ represents NR⁴R⁵ or a 1C-5C alkylgroup; R² and R⁴ each represent a 1C-5C alkyl group or hydrogen atom;and R³ and R⁵ each represent a 1C-5C alkyl group); or (b)HSiCl(NR¹R²)(NR³R⁴), wherein R¹ and R³ independently represent an alkylgroup having 1 to 4 carbon atoms, or a hydrogen atom; and R² and R⁴independently represent an alkyl group having 1 to 4 carbon atoms. Theorganic silicon compounds contained H—Si bonds.

U.S. Pat. No. 5,424,095 describes a method to reduce the rate of cokeformation during the industrial pyrolysis of hydrocarbons, the interiorsurface of a reactor is coated with a uniform layer of a ceramicmaterial, the layer being deposited by thermal decomposition of anon-alkoxylated organosilicon precursor in the vapor phase, in a steamcontaining gas atmosphere in order to form oxide ceramics.

U. S. Publ. No. 2012/0291321 describes a PECVD process for forming ahigh-quality Si carbonitride barrier dielectric film between adielectric film and a metal interconnect of an integrated circuitsubstrate, comprising the steps of: providing an integrated circuitsubstrate having a dielectric film or a metal interconnect; contactingthe substrate with a barrier dielectric film precursor comprising:R_(x)R_(y)(NRR′)_(z)Si wherein R, R′, R and R′ are each individuallyselected from H, linear or branched saturated or unsaturated alkyl, oraromatic group; wherein x+y+z=4; z=1 to 3; but R, R′ cannot both be H;and where z=1 or 2 then each of x and y are at least 1; forming the Sicarbonitride barrier dielectric film with C/Si ratio >0.8 and a N/Siratio >0.2 on the integrated circuit substrate.

U. S. Publ. No. 2013/0295779 A describes an atomic layer deposition(ALD) process for forming a silicon oxide film at a depositiontemperature >500° C. using silicon precursors having the followingformula:R¹R² _(m)Si(NR³R⁴)_(n)X_(p)  I.wherein R¹, R², and R³ are each independently selected from hydrogen, alinear or branched C₁ to C₁₀ alkyl group, and a C₆ to C₁₀ aryl group; R⁴is selected from, a linear or branched C₁ to C₁₀ alkyl group, and a C₆to C₁₀ aryl group, a C₃ to C₁₀ alkylsilyl group; wherein R³ and R⁴ arelinked to form a cyclic ring structure or R³ and R⁴ are not linked toform a cyclic ring structure; X is a halide selected from the groupconsisting of Cl, Br and I; m is 0 to 3; n is 0 to 2; and p is 0 to 2and m+n+p=3; andR¹R² _(m)Si(OR³)_(n)(OR⁴)_(q)X_(p)  II.wherein R¹ and R² are each independently selected from hydrogen, alinear or branched C₁ to C₁₀ alkyl group, and a C₆ to C₁₀ aryl group; R³and R⁴ are each independently selected from a linear or branched C₁ toC₁₀ alkyl group, and a C₆ to C₁₀ aryl group; wherein R³ and R⁴ arelinked to form a cyclic ring structure or R³ and R⁴ are not linked toform a cyclic ring structure; X is a halide atom selected from the groupconsisting of Cl, Br and I; m is 0 to 3; n is 0 to 2; q is 0 to 2 and pis 0 to 2 and m+n+q+p=3

U.S. Pat. No. 7,084,076 discloses a halogenated siloxane such ashexachlorodisiloxane (HCDSO) that is used in conjunction with pyridineas a catalyst for ALD deposition below 500° C. to form silicon dioxide.

U.S. Pat. No. 6,992,019 discloses a method for catalyst-assisted atomiclayer deposition (ALD) to form a silicon dioxide layer having superiorproperties on a semiconductor substrate by using a first reactantcomponent consisting of a silicon compound having at least two siliconatoms, or using a tertiary aliphatic amine as the catalyst component, orboth in combination, together with related purging methods andsequencing. The precursor used is hexachlorodisilane. The depositiontemperature is between 25-150° C.

The disclosures of the previously identified patents, patentapplications and other publications are hereby incorporated byreference.

The above-mentioned prior art, however, still suffers from certaindrawbacks as there still remains a need to develop a process for forminga silicon oxide film having at least one or more of the followingattributes: a density of about 2.1 g/cc or greater, a growth rate of 1.0Å/cycle or greater during the deposition, low chemical impurity, and/orhigh conformality in a thermal atomic layer deposition, a plasmaenhanced atomic layer deposition (ALD) process or a plasma enhancedALD-like process using cheaper, reactive, and more stable siliconprecursor compounds. In addition, there is a need to develop precursorsthat can provide tunable films for example, ranging from silicon oxideto carbon doped silicon oxide.

BRIEF SUMMARY OF THE INVENTION

Described herein is a process for the deposition of a stoichiometric ornonstoichiometric silicon oxide material or film, such as withoutlimitation, a silicon oxide, a carbon doped silicon oxide, a siliconoxynitride film, or a carbon doped silicon oxynitride film at relativelylow temperatures, e.g., at one or more temperatures of 300° C. or loweror, in other embodiments, at relatively high temperatures, e.g., at oneor more temperatures of 600° C. or higher, in a plasma enhanced ALD,plasma enhanced cyclic chemical vapor deposition (PECCVD), a plasmaenhanced ALD-like process, or an ALD process with oxygen-containingreactant source.

In one aspect, there is provided a method to deposit a film comprisingsilicon and oxide onto a substrate which comprises the steps of:

-   -   a) providing a substrate in a reactor;    -   b) introducing into the reactor at least one silicon precursor        compound, wherein the at least one silicon precursor compound        has at least one Si—O—Si linkages is selected from the group        consisting of Formulae A and B:

-   -    wherein R¹ is independently selected from a linear C₁ to C₁₀        alkyl group, a branched C₃ to C₁₀ alkyl group, a C₃ to C₁₀        cyclic alkyl group, a C₃ to C₁₀ heterocyclic group, a C₃ to C₁₀        alkenyl group, a C₃ to C₁₀ alkynyl group, and a C₄ to C₁₀ aryl        group; R² is selected from the group consisting of hydrogen, a        C₁ to C₁₀ linear alkyl group, a branched C₃ to C₁₀ alkyl group,        a C₃ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ heterocyclic group,        a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, and a C₄        to C₁₀ aryl group, wherein R¹ and R² in Formula A or B are        either linked to form a cyclic ring structure or are not linked        to form a cyclic ring structure; R³⁻⁸ are each independently        selected from hydrogen, a linear C₁ to C₁₀ alkyl group, a        branched C₃ to C₁₀ alkyl group, a C₃ to C₁₀ cyclic alkyl group,        a C₂ to C₁₀ alkenyl group, a C₂ to C₁₀ alkynyl group, and a C₄        to C₁₀ aryl group; X is selected from the group consisting of        hydrogen, a linear C₁ to C₁₀ alkyl group, a branched C₃ to C₁₀        alkyl group, a C₃ to C₁₀ cyclic alkyl group, a C₂ to C₁₀ alkenyl        group, a C₂ to C₁₀ alkynyl group, a C₄ to C₁₀ aryl group, halide        (Cl, Br, I), and NR⁹R¹⁰ where R⁹ and R¹⁰ are each independently        selected from hydrogen, a C₁ to C₆ linear alkyl group, a        branched C₃ to C₆ alkyl group, a C₃ to C₁₀ cyclic alkyl group, a        C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynyl group, and a C₄ to        C₁₀ aryl group, wherein R⁹ and R¹⁰ are either linked to form a        cyclic ring structure or are not linked to form a cyclic ring        structure, and wherein R¹ and R⁹ are either linked to form a        cyclic ring or are not linked to form a cyclic ring;    -   c) purging the reactor with a purge gas;    -   d) introducing an oxygen-containing source into the reactor; and    -   e) purging the reactor with the purge gas,    -   wherein the steps b through e are repeated until a desired        thickness of film is deposited; and wherein the method is        conducted at one or more temperatures ranging from about 25° C.        to 600° C.

In this or other embodiments, the oxygen-containing source is a sourceselected from the group consisting of an oxygen plasma, ozone, a watervapor, water vapor plasma, nitrogen oxide (e.g., N₂O, NO, NO₂) plasmawith or without inert gas, a carbon oxide (e.g., CO₂, CO) plasma andcombinations thereof. In certain embodiments, the oxygen-containingsource further comprises an inert gas. In these embodiments, the inertgas is selected from the group consisting of argon, helium, nitrogen,hydrogen, and combinations thereof. In an alternative embodiment, theoxygen-containing source does not comprise an inert gas. In yet anotherembodiment, the oxygen-containing source comprises nitrogen which reactswith the reagents under plasma conditions to provide a siliconoxynitride film.

In one or more embodiments described above, the oxygen-containing plasmasource is selected from the group consisting of oxygen plasma with orwithout inert gas, water vapor plasma with or without inert gas,nitrogen oxides (N₂O, NO, NO₂) plasma with or without inert gas, carbonoxides (CO₂, CO) plasma with or without inert gas, and combinationsthereof. In certain embodiments, the oxygen-containing plasma sourcefurther comprises an inert gas. In these embodiments, the inert gas isselected from the group consisting of argon, helium, nitrogen, hydrogen,or combinations thereof. In an alternative embodiment, theoxygen-containing plasma source does not comprise an inert gas.

One embodiment of the invention relates to a composition for depositinga film selected from a silicon oxide or a carbon doped silicon oxidefilm using a vapor deposition process, the composition comprising: atleast one silicon precursor comprising a compound having the followingFormulae A and B:

wherein R¹ is independently selected from a linear C₁ to C₁₀ alkylgroup, a branched C₃ to C₁₀ alkyl group, a C₃ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ heterocyclic group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀alkynyl group, and a C₄ to C₁₀ aryl group; R² is selected from the groupconsisting of hydrogen, a C₁ to C₁₀ linear alkyl group, a branched C₃ toC₁₀ alkyl group, a C₃ to C₁₀ cyclic alkyl group, a C₃ to C₁₀heterocyclic group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aryl group, wherein R¹ and R² in Formula A or Bare either linked to form a cyclic ring structure or are not linked toform a cyclic ring structure; R³⁻⁹ are each independently selected fromhydrogen, a linear C₁ to C₁₀ alkyl group, a branched C₃ to C₁₀ alkylgroup, a C₃ to C₁₀ cyclic alkyl group, a C₂ to C₁₀ alkenyl group, a C₂to C₁₀ alkynyl group, and a C₄ to C₁₀ aryl group; X is selected from thegroup consisting of hydrogen, a linear C₁ to C₁₀ alkyl group, a branchedC₃ to C₁₀ alkyl group, a C₃ to C₁₀ cyclic alkyl group, a C₂ to C₁₀alkenyl group, a C₂ to C₁₀ alkynyl group, a C₄ to C₁₀ aryl group, halide(Cl, Br, I), and NR⁹R¹⁰ where R⁹ and R¹⁰ are each independently selectedfrom hydrogen, a C₁ to C₆ linear alkyl group, a branched C₃ to C₆ alkylgroup, a C₃ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃to C₁₀ alkynyl group, and a C₄ to C₁₀ aryl group, wherein R⁹ and R¹⁰ areeither linked to form a cyclic ring structure or are not linked to forma cyclic ring structure, and wherein R¹ and R⁹ are either linked to forma cyclic ring or are not linked to form a cyclic ring.

Another embodiment of the invention relates to a silicon oxide filmcomprising at least one of the following characteristics a density of atleast about 2.1 g/cc; a wet etch rate that is less than about 2.5 Å/s asmeasured in a solution of 1:100 of HF to water dilute HF (0.5 wt % dHF)acid; an electrical leakage of less than about 1 e-8 A/cm² up to 6MV/cm; and a hydrogen impurity of less than about 5 e20 at/cc asmeasured by SIMS.

The embodiments of the invention can be used alone or in combinationswith each other.

DETAILED DESCRIPTION OF THE INVENTION

Described herein are compositions and methods related to the formationof a stoichiometric or nonstoichiometric film or material comprisingsilicon and oxide such as, without limitation, a silicon oxide, acarbon-doped silicon oxide film, a silicon oxynitride, a carbon-dopedsilicon oxynitride films or combinations thereof with one or moretemperatures, of about 300° C. or less, or from about 25° C. to about300° C., or from about 250° C. to about 600° C. or from 600 to about800° C. The films described herein are deposited in a deposition processsuch as an atomic layer deposition (ALD) or in an ALD-like process suchas, without limitation, a plasma enhanced ALD or a plasma enhancedcyclic chemical vapor deposition process (CCVD). The low temperaturedeposition (e.g., one or more deposition temperatures ranging from aboutambient temperature to 300° C.) methods described herein provide filmsor materials that exhibit at least one or more of the followingadvantages: a density of about 2.1 g/cc or greater, a growth rate of 1.0Å/cycle or greater, low chemical impurity, high conformality in athermal atomic layer deposition, a plasma enhanced atomic layerdeposition (ALD) process or a plasma enhanced ALD-like process, anability to adjust carbon content in the resulting film; and/or filmshave an etching rate of 5 Angstroms per second ({acute over (Å)}/sec) orless when measured in 0.5 wt % dilute HF. For carbon-doped silicon oxidefilms, greater than 1% carbon is desired to tune the etch rate to valuesbelow 2 {acute over (Å)}/sec in 0.5 wt % dilute HF in addition to othercharacteristics such as, without limitation, a density of about 1.8 g/ccor greater or about 2.0 g/cc or greater.

The instant invention can be practiced using equipment known in the art.For example, the inventive method can use a reactor that is conventionalin the semiconductor manufacturing art.

In one aspect, there is provided a composition comprising at least onesilicon precursor compound having at least one Si—O—Si linkage and atleast one organoamino functionality. Such silicon precursors compoundhas a structure that is represented by either Formulae A and/or B:

wherein R¹ is independently selected from a linear C₁ to C₁₀ alkylgroup, a branched C₃ to C₁₀ alkyl group, a C₃ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ heterocyclic group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀alkynyl group, and a C₄ to C₁₀ aryl group; R² is selected from the groupconsisting of hydrogen, a C₁ to C₁₀ linear alkyl group, a branched C₃ toC₁₀ alkyl group, a C₃ to C₁₀ cyclic alkyl group, a C₃ to C₁₀heterocyclic group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aryl group, wherein R¹ and R² in Formula A or Bare either linked to form a cyclic ring structure or are not linked toform a cyclic ring structure; R³⁻⁸ are each independently selected fromhydrogen, a linear C₁ to C₁₀ alkyl group, a branched C₃ to C₁₀ alkylgroup, a C₃ to C₁₀ cyclic alkyl group, a C₂ to C₁₀ alkenyl group, a C₂to C₁₀ alkynyl group, and a C₄ to C₁₀ aryl group; X is selected from thegroup consisting of hydrogen, a linear C₁ to C₁₀ alkyl group, a branchedC₃ to C₁₀ alkyl group, a C₃ to C₁₀ cyclic alkyl group, a C₂ to C₁₀alkenyl group, a C₂ to C₁₀ alkynyl group, a C₄ to C₁₀ aryl group, halide(Cl, Br, I), and NR⁹R¹⁰ where R⁹ and R¹⁰ are each independently selectedfrom hydrogen, a C₁ to C₆ linear alkyl group, a branched C₃ to C₆ alkylgroup, a C₃ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃to C₁₀ alkynyl group, and a C₄ to C₁₀ aryl group, wherein R⁹ and R¹⁰ areeither linked to form a cyclic ring structure or are not linked to forma cyclic ring structure, and wherein R¹ and R⁹ are either linked to forma cyclic ring or are not linked to form a cyclic ring;

In another aspect, there is provided a composition comprising: (a) atleast one silicon precursor compound having at least one Si—O—Si linkageand at least one organoamino functionality. Such silicon precursorscompound has a structure that is represented by either Formulae A or B:

wherein R¹ is independently selected from a linear C₁ to C₁₀ alkylgroup, a branched C₃ to C₁₀ alkyl group, a C₃ to C₁₀ cyclic alkyl group,a C₃ to C₁₀ heterocyclic group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀alkynyl group, and a C₄ to C₁₀ aryl group; R² is selected from the groupconsisting of hydrogen, a C₁ to C₁₀ linear alkyl group, a branched C₃ toC₁₀ alkyl group, a C₃ to C₁₀ cyclic alkyl group, a C₃ to C₁₀heterocyclic group, a C₃ to C₁₀ alkenyl group, a C₃ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aryl group, wherein R¹ and R² in Formula A or Bare either linked to form a cyclic ring structure or are not linked toform a cyclic ring structure; R³⁻⁸ are each independently selected fromhydrogen, a linear C₁ to C₁₀ alkyl group, a branched C₃ to C₁₀ alkylgroup, a C₃ to C₁₀ cyclic alkyl group, a C₂ to C₁₀ alkenyl group, a C₂to C₁₀ alkynyl group, and a C₄ to C₁₀ aryl group; X is selected from thegroup consisting of hydrogen, a linear C₁ to C₁₀ alkyl group, a branchedC₃ to C₁₀ alkyl group, a C₃ to C₁₀ cyclic alkyl group, a C₂ to C₁₀alkenyl group, a C₂ to C₁₀ alkynyl group, a C₄ to C₁₀ aryl group, halide(Cl, Br, I), and NR⁹R¹⁰ where R⁹ and R¹⁰ are each independently selectedfrom hydrogen, a C₁ to C₆ linear alkyl group, a branched C₃ to C₆ alkylgroup, a C₃ to C₁₀ cyclic alkyl group, a C₃ to C₁₀ alkenyl group, a C₃to C₁₀ alkynyl group, and a C₄ to C₁₀ aryl group, wherein R⁹ and R¹⁰ areeither linked to form a cyclic ring structure or are not linked to forma cyclic ring structure, and wherein R¹ and R⁹ are either linked to forma cyclic ring or are not linked to form a cyclic ring; and (b) asolvent. In certain embodiments of the composition described herein,exemplary solvents can include, without limitation, ether, tertiaryamine, alkyl hydrocarbon, aromatic hydrocarbon, tertiary aminoether, andcombinations thereof. In certain embodiments, the difference between theboiling point of the silicon precursor and the boiling point of thesolvent is 40° C. or less.

In one embodiment of the method described herein, the method isconducted via an ALD process that uses an oxygen-containing source whichcomprises ozone or a plasma wherein the plasma can further comprise aninert gas such as one or more of the following: an oxygen plasma with orwithout inert gas, a water vapor plasma with or without inert gas, anitrogen oxide (e.g., N₂O, NO, NO₂) plasma with or without inert gas, acarbon oxide (e.g., CO₂, CO) plasma with or without inert gas, andcombinations thereof. In this embodiment, the method for depositing asilicon oxide film on at least one surface of a substrate comprises thefollowing steps:

-   -   a) providing a substrate in a reactor;    -   b) introducing into the reactor at least one silicon precursor        having Formulae A or B described herein;    -   c) purging the reactor with purge gas;    -   d) introducing oxygen-containing source comprising a plasma into        the reactor; and    -   e) purging the reactor with a purge gas.

In the method described above, steps b through e are repeated until adesired thickness of film is deposited on the substrate. Theoxygen-containing plasma source can be generated in situ or,alternatively, remotely. In one particular embodiment, theoxygen-containing source comprises oxygen and is flowing, or introducedduring method steps b through d, along with other reagents such aswithout limitation, the at least one silicon precursor and optionally aninert gas.

In another aspect, there is provided a method for depositing asilicon-containing film, the method comprising:

placing a substrate comprising a surface feature into a reactor whereinthe substrate is maintained at one or more temperatures ranging fromabout −20° C. to about 400° C. and a pressure of the reactor ismaintained at 100 torr or less;

introducing at least one silicon precursor having Formulae A or Bdescribed herein;

providing an oxygen-containing source into the reactor to react with theat least one compound to form a film and cover at least a portion of thesurface feature;

annealing the film at one or more temperatures of about 100° C. to 1000°C. to coat at least a portion of the surface feature; and

treating the substrate with an oxygen-containing source at one or moretemperatures ranging from about 20° C. to about 1000° C. to form asilicon-containing film on at least a portion of the surface feature. Incertain embodiments, the oxygen-containing source is selected from thegroup consisting of water vapors, water plasma, ozone, oxygen, oxygenplasma, oxygen/helium plasma, oxygen/argon plasma, nitrogen oxidesplasma, carbon dioxide plasma, hydrogen peroxide, organic peroxides, andmixtures thereof. In this or other embodiments, the method steps arerepeated until the surface features are filled with thesilicon-containing film. In embodiments wherein water vapor is employedas an oxygen-containing source, the substrate temperature ranges fromabout −20° C. to about 40° C. or from about −10° C. to about 25° C.

In another embodiment of the method described herein, the method isconducted via an ALD process that uses an oxygen-containing source whichcomprises ozone or a plasma wherein the plasma can further comprise aninert gas such as one or more of the following: an oxygen plasma with orwithout inert gas, a water vapor plasma with or without inert gas, anitrogen oxide (e.g., N₂O, NO, NO₂) plasma with or without inert gas, acarbon oxide (e.g., CO₂, CO) plasma with or without inert gas, andcombinations thereof. In this embodiment, the method for depositing asilicon oxide film on at least one surface of a substrate attemperatures below 300° C., preferably below 150° C. comprises thefollowing steps:

-   -   a) providing a substrate in a reactor;    -   b) introducing into the reactor at least one silicon precursor        having Formulae A or B wherein R³ and R⁴ are both hydrogen;    -   c) purging the reactor with purge gas;    -   d) introducing oxygen-containing source comprising a plasma into        the reactor; and    -   e) purging the reactor with a purge gas.        In the method described above, steps b through e are repeated        until a desired thickness of film is deposited on the substrate.        The oxygen-containing plasma source can be generated in situ or,        alternatively, remotely. In one particular embodiment, the        oxygen-containing source comprises oxygen and is flowing, or        introduced during method steps b through d, along with other        reagents such as without limitation, the at least one silicon        precursor and optionally an inert gas.

Yet, in another embodiment of the method described herein, the method isconducted via an ALD process that uses an oxygen-containing source whichcomprises ozone or a plasma wherein the plasma can further comprise aninert gas such as one or more of the following: an oxygen plasma with orwithout inert gas, a water vapor plasma with or without inert gas, anitrogen oxide (e.g., N₂O, NO, NO₂) plasma with or without inert gas, acarbon oxide (e.g., CO₂, CO) plasma with or without inert gas, andcombinations thereof. In this embodiment, the method for depositing asilicon oxide film on at least one surface of a substrate attemperatures above 600° C. comprises the following steps:

-   -   a) providing a substrate in a reactor;    -   b) introducing into the reactor at least one silicon precursor        having Formulae A or B wherein R³⁻⁸ and X are all methyl groups;    -   c) purging the reactor with purge gas;    -   d) introducing oxygen-containing source comprising a plasma into        the reactor; and    -   e) purging the reactor with a purge gas.

In the method described above, steps b through e are repeated until adesired thickness of film is deposited on the substrate. Theoxygen-containing plasma source can be generated in situ or,alternatively, remotely. In one particular embodiment, theoxygen-containing source comprises oxygen and is flowing, or introducedduring method steps b through d, along with other reagents such aswithout limitation, the at least one silicon precursor and optionally aninert gas.

In one or more embodiments, the at least one silicon precursor comprisesan organoaminodisiloxane compound having the Formula A described above.In one particular embodiment, R³⁻⁶ in the formula comprise a hydrogen orC₁ alkyl group or methyl. Further exemplary precursors are listed inTable 1

TABLE 1 Organoaminodisiloxane Compounds Having one Si—O—Si linkage inFormula A.

In one or more embodiments, the at least one silicon precursor comprisesan organoaminotrisiloxane compound having the Formula B describedherein. In one particular embodiment, R³⁻⁸ in the formula comprise ahydrogen or C₁ alkyl group or methyl. Further exemplary precursors arelisted in Table 2:

TABLE 2 Organoaminotrisiloxane Compounds Having Two Si—O—Si linkages inFormula B.

In the formulas above and throughout the description, the term “alkyl”denotes a linear or branched functional group having from 1 to 10 carbonatoms. Exemplary linear alkyl groups include, but are not limited to,methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Exemplarybranched alkyl groups include, but are not limited to, iso-propyl,iso-butyl, sec-butyl, tert-butyl, iso-pentyl, tert-pentyl, iso-hexyl,and neo-hexyl. In certain embodiments, the alkyl group may have one ormore functional groups attached thereto such as, but not limited to, analkoxy group, a dialkylamino group or combinations thereof, attachedthereto. In other embodiments, the alkyl group does not have one or morefunctional groups attached thereto. The alkyl group may be saturated or,alternatively, unsaturated.

In the formulas above and throughout the description, the term “cyclicalkyl” denotes a cyclic functional group having from 3 to 10 carbonatoms. Exemplary cyclic alkyl groups include, but are not limited to,cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

In the formulas above and throughout the description, the term “alkenylgroup” denotes a group which has one or more carbon-carbon double bondsand has from 2 to 10 or from 2 to 10 or from 2 to 6 carbon atoms.

In the formulas above and throughout the description, the term “alkynylgroup” denotes a group which has one or more carbon-carbon triple bondsand has from 3 to 10 or from 2 to 10 or from 2 to 6 carbon atoms.

In the formulas above and throughout the description, the term “aryl”denotes an aromatic cyclic functional group having from 4 to 10 carbonatoms, from 5 to 10 carbon atoms, or from 6 to 10 carbon atoms.Exemplary aryl groups include, but are not limited to, phenyl, benzyl,chlorobenzyl, tolyl, o-xylyl, 1,2,3-triazolyl, pyrrrolyl, and furanyl.

In the formulas above and throughout the description, the term “amino”denotes an organoamino group having from 1 to 10 carbon atoms derivedfrom an organoamine with formula of HNR¹R². Exemplary amino groupsinclude, but are not limited to, secondary amino groups derived fromsecondary amines such as dimethylamino (Me₂N—), diethyamino (Et₂N—),di-iso-propylamino (^(i)Pr₂N—); primary amino groups derived fromprimary amines such as methylamino (MeNH—), ethylamine (EtNH—),iso-propylamino (^(i)PrNH—), sec-butylamino (^(s)BuNH—), andtert-butylamino (^(t)BuNH—).

The inventive compounds having Formulae A or B can be produced, forexample, by following one or more of the reactions shown in equations(1) to (10):

The reactions in Equations (1) to (12) can be conducted with (e.g., inthe presence of) or without (e.g., in the absence of) organic solvents.In embodiments wherein an organic solvent is used, examples of suitableorganic solvents include, but are not limited to, hydrocarbon such ashexanes, octane, toluene, and ethers such as diethyl ether andtetrahydrofuran (THF). In these or other embodiments, the reactiontemperature is in the range of from about −70° C. to the boiling pointof the solvent employed if a solvent is used or to the boiling point ofthe most volatile component in the reaction. In other embodiments, thereaction temperature can be higher than the normal boiling point of themost volatile component if a high pressure reactor is used. Theresulting silicon precursor compound can be purified, for example, viavacuum distillation after removing all by-products as well as anysolvent(s) if present.

Equations (1) and (2) are one synthetic route to make the siliconprecursor compounds having Formulae A or B involving a reaction betweenhalidodisiloxanes or halidotrisiloxanes and an organoamine. Equations(3) and (4) are one synthetic route to make the silicon precursorcompounds having Formulae A or B involving a dehydrocoupling reactionbetween either hydridodisiloxane or hydridotrisiloxane and anorganoamine in presence of catalyst. Alternatively, in equations (1) to(4), these reactions could be carried out with a metal amide such as,without limitation, lithium amide (LiNR¹R²), sodium amide (NaNR¹R²), orpotassium amide (KNR¹R²) instead of free organoamine (HNR¹R²) in thepresence or absence of a catalyst. The hydridodisiloxane orhydridotrisiloxane starting materials in equations (3) and (4) can besynthesized, for example, by the synthetic routes shown in equations (5)to (8) involving the reaction of a either a silanol, a disiloxanol, or ametallated form of these two (e.g. potassium trimethylsilanolate,potassium pentamethyldisiloxanolate) with either an organoaminosilane ora halidosilane containing at least one Si—H bond. Equations (9) and (10)are another synthetic route to make the silicon precursor compoundshaving Formulae A or B involving the reaction of either a silanol, adisiloxanol, or a metallated form of these two with anorganoaminohalidosilane. Equations (11) and (12) are yet anothersynthetic route to make the silicon precursor compounds having FormulaeA or B involving the reaction of either a silanol, a disiloxanol, or ametallated form of these two with a bis(organoamino)silane. Othersynthetic routes may be also employed to make these silicon precursorcompounds having Formula A or B as disclosed in the prior art, forexample reducing organoaminochlorodisiloxane ororganoaminochlorotrisiloxane with metal hydride such as LiH, LiAlH₄ orreacting hydridodisiloxane or hydridotrisiloxane with imine in thepresence or absence of catalyst (hydrosilylation of imine).

The silicon precursor compounds having Formulae A or B according to thepresent invention and compositions comprising the silicon precursorcompounds having Formulae A or B according to the present invention arepreferably substantially free of halide ions. As used herein, the term“substantially free” as it relates to halide ions (or halides) such as,for example, chlorides, fluorides, bromides, and iodides, means lessthan 5 ppm (by weight), preferably less than 3 ppm, and more preferablyless than 1 ppm, and most preferably 0 ppm. Chlorides are known to actas decomposition catalysts for the silicon precursor compounds havingFormulae A or B. Significant levels of chloride in the final product cancause the silicon precursor compounds to degrade. The gradualdegradation of the silicon precursor compounds may directly impact thefilm deposition process making it difficult for the semiconductormanufacturer to meet film specifications. The silicon precursorcompounds having Formulae A or B are preferably substantially free ofmetal ions such as, Al³⁺ ions, Fe²⁺, Fe³⁺, Ni²⁺, Cr³⁺. As used herein,the term “substantially free” as it relates to Al³⁺ ions, Fe²⁺, Fe³⁺,Ni²⁺, Cr³⁺ means less than 5 ppm (by weight), preferably less than 3ppm, and more preferably less than 1 ppm, and most preferably 0.1 ppm.In some embodiments, the silicon precursor compounds having Formulae Aor B are free of metal ions such as, Al³⁺ ions, Fe²⁺, Fe³⁺, Ni²⁺, Cr³⁺.As used herein, the term “free of” as it relates to Al³⁺ ions, Fe²⁺,Fe³⁺, Ni²⁺, Cr³⁺ means 0 ppm (by weight), In addition, the shelf-life orstability is negatively impacted by the higher degradation rate of thesilicon precursor compounds thereby making it difficult to guarantee a1-2 year shelf-life. Moreover, the silicon precursor compounds are knownto form flammable and/or pyrophoric gases upon decomposition such ashydrogen and disiloxanes or trisiloxanes. Therefore, the accelerateddecomposition of the silicon precursor compounds presents safety andperformance concerns related to the formation of these flammable and/orpyrophoric gaseous byproducts.

For those embodiments wherein the silicon precursor(s) having Formulae Aor B is (are) used in a composition comprising a solvent and a siliconprecursor compounds having Formulae A or B described herein, the solventor mixture thereof selected does not react with the silicon precursor.The amount of solvent by weight percentage in the composition rangesfrom 0.5 wt % by weight to 99.5 wt % or from 10 wt % by weight to 75 wt%. In this or other embodiments, the solvent has a boiling point (b.p.)similar to the b.p. of the silicon precursor of Formula A or B or thedifference between the b.p. of the solvent and the b.p. of the siliconprecuror of Formula A or B is 40° C. or less, 30° C. or less, or 20° C.or less, or 10° C. Alternatively, the difference between the boilingpoints ranges from any one or more of the following end-points: 0, 10,20, 30, or 40° C. Examples of suitable ranges of b.p. difference includewithout limitation, 0 to 40° C., 20° C. to 30° C., or 10° C. to 30° C.Examples of suitable solvents in the compositions include, but are notlimited to, an ether (such as 1,4-dioxane, dibutyl ether), a tertiaryamine (such as pyridine, 1-methylpiperidine, 1-ethylpiperidine,N,N′-Dimethylpiperazine, N,N,N′,N′-Tetramethylethylenediamine), anitrile (such as benzonitrile), an alkyl hydrocarbon (such as octane,nonane, dodecane, ethylcyclohexane), an aromatic hydrocarbon (such astoluene, mesitylene), a tertiary aminoether (such asbis(2-dimethylaminoethyl) ether), or mixtures thereof.

Throughout the description, the term “ALD or ALD-like” refers to aprocess including, but not limited to, the following processes: a) eachreactant including a silicon precursor and a reactive gas is introducedsequentially into a reactor such as a single wafer ALD reactor,semi-batch ALD reactor, or batch furnace ALD reactor; b) each reactantincluding the silicon precursor and the reactive gas is exposed to asubstrate by moving or rotating the substrate to different sections ofthe reactor and each section is separated by inert gas curtain, i.e.,spatial ALD reactor or roll to roll ALD reactor.

Throughout the description, the term “alkyl hydrocarbon” refers a linearor branched C₁ to C₂₀ hydrocarbon, cyclic C₆ to C₂₀ hydrocarbon.Exemplary hydrocarbon includes, but not limited to, heptane, octane,nonane, decane, dodecane, cyclooctane, cyclononane, cyclodecane.Throughout the description, the term “aromatic hydrocarbon” refers a C₆to C₂₀ aromatic hydrocarbon. Exemplary aromatic hydrocarbon includes,but not limited to, toluene, mesitylene.

In certain embodiments, substituents R¹ and R² in the Formulas A and Bcan be linked together to form a ring structure. As the skilled personwill understand, where R¹ and R² are linked together to form a ring andR¹ would include a bond for linking to R² and vice versa. In theseembodiments, the ring structure can be unsaturated such as, for example,a cyclic alkyl ring, or saturated, for example, an aryl ring. Further,in these embodiments, the ring structure can also be substituted orunsubstituted with one or more atoms or groups. Exemplary cyclic ringgroups include, but not limited to, pyrrolyl, pyrrolidino, piperidino,and 2,6-dimethylpiperidino groups. In other embodiments, however,substituent R¹ and R² are not linked to form a ring structure.

In certain embodiments, the silicon oxide or carbon doped silicon oxidefilms deposited using the methods described herein are formed in thepresence of oxygen-containing source comprising ozone, water (H₂O)(e.g., deionized water, purifier water, and/or distilled water), oxygen(C₂), oxygen plasma, NO, N₂O, NO₂, carbon monoxide (CO), carbon dioxide(CO₂) and combinations thereof. The oxygen-containing source is passedthrough, for example, either an in situ or remote plasma generator toprovide oxygen-containing plasma source comprising oxygen such as anoxygen plasma, a plasma comprising oxygen and argon, a plasma comprisingoxygen and helium, an ozone plasma, a water plasma, a nitrous oxideplasma, or a carbon dioxide plasma. In certain embodiments, theoxygen-containing plasma source comprises an oxygen-containing sourcegas that is introduced into the reactor at a flow rate ranging fromabout 1 to about 2000 standard cubic centimeters (sccm) or from about 1to about 1000 sccm. The oxygen-containing plasma source can beintroduced for a time that ranges from about 0.1 to about 100 seconds.In one particular embodiment, the oxygen-containing plasma sourcecomprises water having a temperature of 10° C. or greater. Inembodiments wherein the film is deposited by a PEALD or a plasmaenhanced cyclic CVD process, the precursor pulse can have a pulseduration that is greater than 0.01 seconds (e.g., about 0.01 to about0.1 seconds, about 0.1 to about 0.5 seconds, about 0.5 to about 10seconds, about 0.5 to about 20 seconds, about 1 to about 100 seconds)depending on the ALD reactor's volume, and the oxygen-containing plasmasource can have a pulse duration that is less than 0.01 seconds (e.g.,about 0.001 to about 0.01 seconds).

The deposition methods disclosed herein may involve one or more purgegases. The purge gas, which is used to purge away unconsumed reactantsand/or reaction byproducts, is an inert gas that does not react with theprecursors. Exemplary purge gases include, but are not limited to, argon(Ar), nitrogen (N₂), helium (He), neon, hydrogen (H₂), and mixturesthereof. In certain embodiments, a purge gas such as Ar is supplied intothe reactor at a flow rate ranging from about 10 to about 2000 sccm forabout 0.1 to 1000 seconds, thereby purging the unreacted material andany byproduct that may remain in the reactor.

The respective step of supplying the precursors, oxygen-containingsource, and/or other precursors, source gases, and/or reagents may beperformed by changing the time for supplying them to change thestoichiometric composition of the resulting dielectric film.

Energy is applied to the at least one of the silicon precursor,oxygen-containing source, or combination thereof to induce reaction andto form the dielectric film or coating on the substrate. Such energy canbe provided by, but not limited to, thermal, plasma, pulsed plasma,helicon plasma, high density plasma, inductively coupled plasma, X-ray,e-beam, photon, remote plasma methods, and combinations thereof. Incertain embodiments, a secondary RF frequency source can be used tomodify the plasma characteristics at the substrate surface. Inembodiments wherein the deposition involves plasma, the plasma-generatedprocess may comprise a direct plasma-generated process in which plasmais directly generated in the reactor, or alternatively, a remoteplasma-generated process in which plasma is generated outside of thereactor and supplied into the reactor.

The at least one silicon precursor may be delivered to the reactionchamber such as a plasma enhanced cyclic CVD or PEALD reactor or a batchfurnace type reactor in a variety of ways. In one embodiment, a liquiddelivery system may be utilized. In an alternative embodiment, acombined liquid delivery and flash vaporization process unit may beemployed, such as, for example, the turbo vaporizer manufactured by MSPCorporation of Shoreview, Minn., to enable low volatility materials tobe volumetrically delivered, which leads to reproducible transport anddeposition without thermal decomposition of the precursor. In liquiddelivery formulations, the precursors described herein may be deliveredin neat liquid form, or alternatively, may be employed in solventformulations or compositions comprising same. Thus, in certainembodiments the precursor formulations may include solvent component(s)of suitable character as may be desirable and advantageous in a givenend use application to form a film on a substrate.

For those embodiments wherein the at least one silicon precursordescribed herein is used in a composition comprising a solvent and an atleast one silicon precursor described herein, the solvent or mixturethereof selected does not react with the silicon precursor. The amountof solvent by weight percentage in the composition ranges from 0.5 wt %by weight to 99.5 wt % or from 10 wt % by weight to 75 wt %. In this orother embodiments, the solvent has a boiling point (b.p.) similar to theb.p. of the at least one silicon precursor or the difference between theb.p. of the solvent and the b.p. of the t least one silicon precursor is40° C. or less, 30° C. or less, or 20° C. or less, or 10° C. or less.Alternatively, the difference between the boiling points ranges from anyone or more of the following end-points: 0, 10, 20, 30, or 40° C.Examples of suitable ranges of b.p. difference include withoutlimitation, 0 to 40° C., 20° C. to 30° C., or 10° C. to 30° C. Examplesof suitable solvents in the compositions include, but are not limitedto, an ether (such as 1,4-dioxane, dibutyl ether), a tertiary amine(such as pyridine, 1-methylpiperidine, 1-ethylpiperidine,N,N′-Dimethylpiperazine, N,N,N′,N′-Tetramethylethylenediamine), anitrile (such as benzonitrile), an alkane (such as octane, nonane,dodecane, ethylcyclohexane), an aromatic hydrocarbon (such as toluene,mesitylene), a tertiary aminoether (such as bis(2-dimethylaminoethyl)ether), or mixtures thereof.

As previously mentioned, the purity level of the at least one siliconprecursor is sufficiently high enough to be acceptable for reliablesemiconductor manufacturing. In certain embodiments, the at least onesilicon precursor described herein comprise less than 2% by weight, orless than 1% by weight, or less than 0.5%, or less than 0.1%, or lessthan 0.01% (100 ppm), or 0.001% (10 ppm), or 0.0001 (1 ppm) % by weightof one or more of the following impurities: free amines, free halides orhalogen ions such as chloride (Cl), bromide (Br), and higher molecularweight species. The impurity level of halides (Cl or Br) in the siliconprecursor should be less than 100 ppm, 50 ppm, 20 ppm, 10 ppm, 5 ppm, or1 ppm. Higher purity levels of the silicon precursor described hereincan be obtained through one or more of the following processes:purification, adsorption, and/or distillation.

In one embodiment of the method described herein, a plasma enhancedcyclic deposition process such as PEALD-like or PEALD may be usedwherein the deposition is conducted using the at least one siliconprecursor and an oxygen-containing source. The PEALD-like process isdefined as a plasma enhanced cyclic CVD process but still provides highconformal silicon oxide films.

In certain embodiments, the gas lines connecting from the precursorcanisters to the reaction chamber are heated to one or more temperaturesdepending upon the process requirements and the container of the atleast one silicon precursor is kept at one or more temperatures forbubbling. In other embodiments, a solution comprising the at least onesilicon precursor is injected into a vaporizer kept at one or moretemperatures for direct liquid injection.

A flow of argon and/or other gas may be employed as a carrier gas tohelp deliver the vapor of the at least one silicon precursor to thereaction chamber during the precursor pulsing. In certain embodiments,the reaction chamber process pressure is about 50 mTorr to 10 Torr. Inother embodiments, the reaction chamber process pressure can be up to760 Torr (e.g., about 50 mtorr to about 100 Torr).

In a typical PEALD or a PEALD-like process such as a PECCVD process, thesubstrate such as a silicon oxide substrate is heated on a heater stagein a reaction chamber that is exposed to the silicon precursor initiallyto allow the complex to chemically adsorb onto the surface of thesubstrate.

A purge gas such as argon purges away unabsorbed excess complex from theprocess chamber. After sufficient purging, an oxygen-containing sourcemay be introduced into reaction chamber to react with the absorbedsurface followed by another gas purge to remove reaction by-productsfrom the chamber. The process cycle can be repeated to achieve thedesired film thickness. In some cases, pumping can replace a purge withinert gas or both can be employed to remove unreacted siliconprecursors.

In this or other embodiments, it is understood that the steps of themethods described herein may be performed in a variety of orders, may beperformed sequentially, may be performed concurrently (e.g., during atleast a portion of another step), and any combination thereof. Therespective step of supplying the precursors and the oxygen-containingsource gases may be performed by varying the duration of the time forsupplying them to change the stoichiometric composition of the resultingdielectric film. Also, purge times after precursor or oxidant steps canbe minimized to <0.1 s so that throughput is improved.

One particular embodiment of the method described herein to deposit ahigh quality silicon oxide film on a substrate at temperatures less than300° C. comprises the following steps:

-   -   a. providing a substrate in a reactor;    -   b. introducing into the reactor at least one silicon precursor        having the Formulae A or B wherein the silicon precursor having        one SiH₂ group connected to an organoamino functionality        described herein;    -   c. purging reactor with purge gas to remove at least a portion        of the unabsorbed precursors;    -   d. introducing an oxygen-containing plasma source into the        reactor and    -   e. purging reactor with purge gas to remove at least a portion        of the unreacted oxygen-containing source, wherein steps b        through e are repeated until a desired thickness of the silicon        oxide film is deposited. It is believed that the silicon        precursor having one SiH₂ group is anchored onto a surface        having hydroxyl group via releasing organoamine and the small        SiH₂ groups allow more silicon fragments to be anchored compared        the silicon precursor having SiHMe or SiMe₂ connected to an        organoamino functionality, thus achieving growth rates higher        than 1.5 Å/cycle.

Another particular embodiment of the method described herein to deposita high quality silicon oxide film on a substrate at temperatures greaterthan 600° C. comprises the following steps:

-   -   a. providing a substrate in a reactor;    -   b. introducing into the reactor at least one silicon precursor        having the Formulae A or B wherein R³⁻⁸ and X are all methyl        described herein;    -   c. purging reactor with purge gas to remove at least a portion        of the unabsorbed precursors;    -   d. introducing an oxygen-containing plasma source into the        reactor and    -   e. purging reactor with purge gas to remove at least a portion        of the unreacted oxygen-containing source,        wherein steps b through e are repeated until a desired thickness        of the silicon oxide film is deposited. It is believed that        Si-methyl groups are stable at temperatures higher than 600° C.,        thus preventing any chemical vapor deposition due to thermal        decomposition of the silicon precursors such as those having        Si—H groups and allowing high temperature deposition of high        quality silicon oxide possible.

Yet another method disclosed herein forms a carbon doped silicon oxidefilms using an organoaminodisiloxane compound or anorganoaminotrisiloxane compound and an oxygen-containing source.

A still further exemplary process is described as follows:

-   -   a. Providing a substrate in a reactor    -   b. Contacting vapors generated from an organoaminodisiloxane        compound or an organoaminotrisiloxane compound having Formulae A        or B described herein with or without co-flowing an        oxygen-containing source to chemically sorb the precursors on        the heated substrate;    -   c. Purging away any unabsorbed precursors;    -   d. Introducing an oxygen-containing source on the heated        substrate to react with the sorbed precursors; and,    -   e. Purging away any unreacted oxygen-containing source, wherein        steps b through e are repeated until a desired thickness is        achieved.

Various commercial ALD reactors such as single wafer, semi-batch, batchfurnace or roll to roll reactor can be employed for depositing the solidsilicon oxide or carbon doped silicon oxide.

In one embodiment, process temperature for the method described hereinuse one or more of the following temperatures as endpoints: 0, 25, 50,75, 100, 125, 150, 175, 200, 225, 250, 275, and 300° C. Exemplarytemperature ranges include, but are not limited to the following: fromabout 0° C. to about 300° C.; or from about 25° C. to about 300° C.; orfrom about 50° C. to about 290° C.; or from about 25° C. to about 250°C., or from about 25° C. to about 200° C. In other embodiment, theprocess temperature for the method described herein use one or more ofthe following temperatures as endpoints: 300, 325, 350, 375, 400, 425,450, 475, 500, 525, 550, 575, and 600° C. Yet, in other embodiment, theprocess temperature for the method described herein use one or more ofthe following temperatures as endpoints: 600, 625, 650, 675, 700, 725,750, 775, and 800° C. Depending on the structures of the siliconprecursors, some are suitable for deposition at temperatures less than600° C. while others may be more suitable for temperatures higher than600° C. For example, the silicon precursors having Formulae A or Bwherein R³ and R⁴ are both hydrogen are suitable for deposition of highquality silicon oxide at temperatures less than 600° C., on the otherhand, the silicon precursor having Formulae A or B wherein R³⁻⁸ and Xare all methyl groups can be used for deposition of high quality siliconoxide at temperatures ranging from room temperature to 800° C.,especially for temperatures higher than 600° C. because Si-Me groups aremore resistance to oxidation than Si—H groups. It is believed thatSi-methyl groups are stable at temperatures higher than 600° C., thuspreventing any chemical vapor deposition due to thermal decomposition ofthe silicon precursors such as those having Si—H groups and allowinghigh temperature deposition of high quality silicon oxide possible.

In a still further embodiment of the method described herein, the filmor the as-deposited film is subjected to a treatment step. The treatmentstep can be conducted during at least a portion of the deposition step,after the deposition step, and combinations thereof. Exemplary treatmentsteps include, without limitation, treatment via high temperaturethermal annealing; plasma treatment; ultraviolet (UV) light treatment;laser; electron beam treatment and combinations thereof to affect one ormore properties of the film. The films deposited with the siliconprecursors having Formulae A or B described herein, when compared tofilms deposited with previously disclosed silicon precursors under thesame conditions, have improved properties such as, without limitation, awet etch rate that is lower than the wet etch rate of the film beforethe treatment step or a density that is higher than the density prior tothe treatment step. In one particular embodiment, during the depositionprocess, as-deposited films are intermittently treated. Theseintermittent or mid-deposition treatments can be performed, for example,after each ALD cycle, after every a certain number of ALD, such as,without limitation, one (1) ALD cycle, two (2) ALD cycles, five (5) ALDcycles, or after every ten (10) or more ALD cycles.

In an embodiment wherein the film is treated with a high temperatureannealing step, the annealing temperature is at least 100° C. or greaterthan the deposition temperature. In this or other embodiments, theannealing temperature ranges from about 400° C. to about 1000° C. Inthis or other embodiments, the annealing treatment can be conducted in avacuum (<760 Torr), inert environment or in oxygen containingenvironment (such as H₂O, N₂O, NO₂ or C₂).

In an embodiment wherein the film is treated to UV treatment, film isexposed to broad band UV or, alternatively, an UV source having awavelength ranging from about 150 nanometers (nm) to about 400 nm. Inone particular embodiment, the as-deposited film is exposed to UV in adifferent chamber than the deposition chamber after a desired filmthickness is reached.

In an embodiment where in the film is treated with a plasma, passivationlayer such as SiO₂ or carbon doped SiO₂ is deposited to prevent chlorineand nitrogen contamination to penetrate into film in the subsequentplasma treatment. The passivation layer can be deposited using atomiclayer deposition or cyclic chemical vapor deposition.

In an embodiment wherein the film is treated with a plasma, the plasmasource is selected from the group consisting of hydrogen plasma, plasmacomprising hydrogen and helium, plasma comprising hydrogen and argon.Hydrogen plasma lowers film dielectric constant and boost the damageresistance to following plasma ashing process while still keeping thecarbon content in the bulk almost unchanged.

It is believed that the silicon precursors having Formulae A or B can beanchored on substrate surface to provide Si—O—Si or Si—O—Si—O—Sifragments, thus boosting the growth rate of silicon oxide or carbondoped silicon oxide compared to conventional silicon precursors such asbis(tert-butylamino)silane or bis(diethylamino)silane having only onesilicon atom. Importantly the as deposited Si—O—Si or Si—O—Si—O—Sifragments in a given pulse of the silicon precursors can provide betterprotection to the substrate, potentially avoiding or reducing substrateoxidation in the subsequent pulse of the oxygen-containing source duringALD process because conventional silicon precursors such asbis(tert-butylamino)silane or bis(diethylamino)silane can only provide asingle layer of silicon fragments.

In certain embodiments, the silicon precursors having Formula A or Bdescribed herein can also be used as a dopant for metal containingfilms, such as but not limited to, metal oxide films or metal nitridefilms. In these embodiments, the metal containing film is depositedusing an ALD or CVD process such as those processes described hereinusing metal alkoxide, metal amide, or volatile organometallicprecursors. Examples of suitable metal alkoxide precursors that may beused with the method disclosed herein include, but are not limited to,group 3 to 6 metal alkoxide, group 3 to 6 metal complexes having bothalkoxy and alkyl substituted cyclopentadienyl ligands, group 3 to 6metal complexes having both alkoxy and alkyl substituted pyrrolylligands, group 3 to 6 metal complexes having both alkoxy and diketonateligands; group 3 to 6 metal complexes having both alkoxy and ketoesterligands; Examples of suitable metal amide precursors that may be usedwith the method disclosed herein include, but are not limited to,tetrakis(dimethylamino)zirconium (TDMAZ),tetrakis(diethylamino)zirconium (TDEAZ),tetrakis(ethylmethylamino)zirconium (TEMAZ),tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium(TDEAH), and tetrakis(ethylmethylamino)hafnium (TEMAH),tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium(TDEAT), tetrakis(ethylmethylamino)titanium (TEMAT), tert-butyliminotri(diethylamino)tantalum (TBTDET), tert-butyliminotri(dimethylamino)tantalum (TBTDMT), tert-butyliminotri(ethylmethylamino)tantalum (TBTEMT), ethyliminotri(diethylamino)tantalum (EITDET), ethyliminotri(dimethylamino)tantalum (EITDMT), ethyliminotri(ethylmethylamino)tantalum (EITEMT), tert-amyliminotri(dimethylamino)tantalum (TAIMAT), tert-amyliminotri(diethylamino)tantalum, pentakis(dimethylamino)tantalum,tert-amylimino tri(ethylmethylamino)tantalum,bis(tert-butylimino)bis(dimethylamino)tungsten (BTBMW),bis(tert-butylimino)bis(diethylamino)tungsten,bis(tert-butylimino)bis(ethylmethylamino)tungsten, and combinationsthereof. Examples of suitable organometallic precursors that may be usedwith the method disclosed herein include, but are not limited to, group3 metal cyclopentadienyls or alkyl cyclopentadienyls. Exemplary Group 3to 6 metals herein include, but not limited to, Y, La, Ce, Pr, Nd, Sm,Eu, Gd, Tb, Dy, Er, Yb, Lu, Ti, Hf, Zr, V, Nb, Ta, Cr, Mo, and W.

In certain embodiments, the resultant silicon-containing films orcoatings can be exposed to a post-deposition treatment such as, but notlimited to, a plasma treatment, chemical treatment, ultraviolet lightexposure, electron beam exposure, and/or other treatments to affect oneor more properties of the film.

In certain embodiments, the silicon-containing films described hereinhave a dielectric constant of 6 or less, 5 or less, 4 or less, and 3 orless. In these or other embodiments, the films can a dielectric constantof about 5 or below, or about 4 or below, or about 3.5 or below.However, it is envisioned that films having other dielectric constants(e.g., higher or lower) can be formed depending upon the desired end-useof the film. An example of silicon-containing film that is formed usingthe silicon precursors having Formula A or B precursors and processesdescribed herein has the formulation Si_(x)O_(y)C_(z)N_(v)H_(w) whereinSi ranges from about 10% to about 40%; 0 ranges from about 0% to about65%; C ranges from about 0% to about 75% or from about 0% to about 50%;N ranges from about 0% to about 75% or from about 0% to 50%; and Hranges from about 0% to about 50% atomic percent weight % whereinx+y+z+v+w=100 atomic weight percent, as determined for example, by XPSor other means. Another example of the silicon containing film that isformed using the organoaminodisiloxane or organoaminotrisiloxaneprecursors having Formulae A or B and processes described herein issilicon carbonitride wherein the carbon content is from 1 at % to 80 at% measured by XPS. In yet, another example of the silicon containingfilm that is formed using the organoaminodisiloxanes ororganoaminotrisiloxanes precursors having Formulae A or B and processesdescribed herein is amorphous silicon wherein both sum of nitrogen andcarbon contents is <10 at %, preferably <5 at %, most preferably <1 at %measured by XPS.

As mentioned previously, the method described herein may be used todeposit a silicon-containing film on at least a portion of a substrate.Examples of suitable substrates include but are not limited to, silicon,SiO₂, Si₃N₄, OSG, FSG, silicon carbide, hydrogenated silicon carbide,silicon nitride, hydrogenated silicon nitride, silicon carbonitride,hydrogenated silicon carbonitride, boronitride, antireflective coatings,photoresists, germanium, germanium-containing, boron-containing, Ga/As,a flexible substrate, organic polymers, porous organic and inorganicmaterials, metals such as copper and aluminum, and diffusion barrierlayers such as but not limited to TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, orWN. The films are compatible with a variety of subsequent processingsteps such as, for example, chemical mechanical planarization (CMP) andanisotropic etching processes.

The deposited films have applications, which include, but are notlimited to, computer chips, optical devices, magnetic informationstorages, coatings on a supporting material or substrate,microelectromechanical systems (MEMS), nanoelectromechanical systems,thin film transistor (TFT), light emitting diodes (LED), organic lightemitting diodes (OLED), IGZO, and liquid crystal displays (LCD).Potential use of resulting solid silicon oxide or carbon doped siliconoxide include, but not limited to, shallow trench insulation, interlayer dielectric, passivation layer, an etch stop layer, part of a dualspacer, and sacrificial layer for patterning.

The methods described herein provide a high quality silicon oxide orcarbon-doped silicon oxide film. The term “high quality” means a filmthat exhibits one or more of the following characteristics: a density ofabout 2.1 g/cc or greater, 2.2 g/cc or greater, 2.25 g/cc or greater; awet etch rate that is 2.5 Å/s or less, 2.0 Å/s or less, 1.5 Å/s or less,1.0 Å/s or less, 0.5 Å/s or less, 0.1 Å/s or less, 0.05 Å/s or less,0.01 Å/s or less as measured in a solution of 1:100 of HF to waterdilute HF (0.5 wt % dHF) acid, an electrical leakage of about 1 or lesse-8 A/cm² up to 6 MV/cm); a hydrogen impurity of about 5 e20 at/cc orless as measured by SIMS; and combinations thereof. With regard to theetch rate, a thermally grown silicon oxide film has 0.5 Å/s etch rate in0.5 wt % Hf.

In certain embodiments, one or more silicon precursors having Formulae Aor B described herein can be used to form silicon oxide films that aresolid and are non-porous or are substantially free of pores.

The following examples illustrate the method for depositing siliconoxide films described herein and are not intended to limit it in anyway.

EXAMPLES

Thermal atomic layer deposition of silicon oxide films were performed ona laboratory scale ALD processing tool. The silicon precursor wasdelivered to the chamber by vapor draw. All gases (e.g., purge andreactant gas or precursor and oxygen-containing source) were preheatedto 100° C. prior to entering the deposition zone. Gases and precursorflow rates were controlled with ALD diaphragm valves with high speedactuation. The substrates used in the deposition were 12 inch longsilicon strips. A thermocouple attached on the sample holder to confirmsubstrate temperature. Depositions were performed using ozone asoxygen-containing source gas. Normal deposition process and parametersare shown in Table 4. Thickness and refractive indices of the films weremeasured using a FilmTek 2000SE ellipsometer by fitting the reflectiondata from the film to a pre-set physical model (e.g., the LorentzOscillator model).

All plasma enhanced ALD (PEALD) was performed on a commercial stylelateral flow reactor (300 mm PEALD tool manufactured by ASM) equippedwith 27.1 MHz direct plasma capability with 3.5 mm fixed spacing betweenelectrodes. The design utilizes outer and inner chambers which haveindependent pressure settings. The inner chamber is the depositionreactor in which all reactant gases (e.g. precursor, Ar) are mixed inthe manifold and delivered to the process reactor. Ar gas is used tomaintain reactor pressure in the outer chamber. All precursors wereliquids maintained at room temperature in stainless steel bubblers anddelivered to the chamber with Ar carrier gas, typically set at 200 sccmflow. All depositions reported in this study were done on native oxidecontaining Si substrates of 8-12 Ohm-cm. A Rudolph FOCUS EllipsometerFE-IVD (Rotating Compensator Ellipsometer) was used to measure filmthickness and refractive index (RI).

Example 1: Synthesis of 1-di-iso-propylamino-3,3,3-trimethyldisiloxane

A solution of potassium trimethylsilanolate in diethyl ether and THF wasadded dropwise to a stirred solution of 1 equivalentdi-iso-propylaminochlorosilane in THF. After 20 minutes, the solidprecipitate was removed by filtration and the filtrate was concentratedunder reduced pressure. The resulting liquid contained1-di-iso-propylamino-3,3,3-trimethyldisiloxane among other products asdetermined by GC-MS. GC-MS showed the following mass peaks: 219 (M+),204 (M-15), 188, 174, 162, 146, 132, 119, 105, 89, 73, 59.

Example 2: Synthesis of1,3-bis(dimethylamino)-1,1,3,3-tetramethyldisiloxane

A solution of trimethylamine and dimethylamine in THF and hexanes waschilled to below 0° C. 1,3-dichlorotetramethyldisiloxane was slowlyadded dropwise to the this solution while stirring. The solids wereremoved by filtration and the filtrate was purified by vacuumdistillation to provide1,3-bis(dimethylamino)-1,1,3,3-tetramethyldisiloxane (56° C./5 Torr).GC-MS showed the following mass peaks: 220 (M+), 205 (M-15), 196, 175,162, 146, 133, 119, 102.

Examples 3-10: Synthesis of Additional Organoaminodisiloxanes, orOrganoaminotrisiloxanes

Additional organoaminodisiloxanes, or organoaminotrisiloxanes weresynthesized via similar fashion as described in Examples 1 and 2 andwere characterized by GC-MS. The molecular weight (MW), the structure,and corresponding major MS fragmentation peaks of each compound areprovided in Table 3 to confirm their identification.

TABLE 3 Organoaminodisiloxanes and Organoaminotrisiloxanes Ex. PrecursorName MW Structure MS Peaks 3 1,3-Bis(tert-butylamino)- disiloxane 220.46

220, 205, 189, 178, 147, 132, 118, 107 4 1,3-bis(di-isopropylamino)-1,3-dimethyldisiloxane 304.62

304, 289, 202, 188, 160, 146, 119, 105 5 1,3-Bis(diethylamino)-1,1,3,3-tetramethyldisiloxane 276.57

276, 261, 245, 231, 204, 190, 174, 160, 133, 119 61-Disecbutylamino-3-chloro- 1,1,3,3-tetramethyldisiloxane 296.00

295, 281, 265, 249, 235, 221, 207, 193, 177, 163, 147, 133, 119, 103 71,5-Bis(tert- butylamino)trisiloxane 266.56

266, 251, 243, 235, 224, 193, 178, 153, 8 1,5-bis(di-iso-propylamino)-1,3,5-trimethyltrisiloxane 364.75

364, 349, 362, 248, 220, 206, 180, 165, 149, 133, 119, 105 91-dimethylamino-1,1,3,3,3- pentamethyldisiloxane 191.42

191, 176, 160, 147, 133, 117, 103, 88 10 1-dimethylamino-1,3,3,3-tetramethyldisiloxane 177.39

177, 162, 146, 133, 119, 103, 89

Comparative Example 11a: Thermal Atomic Layer Deposition of SiliconOxide Films with Dimethylaminotrimethylsilane (DMATMS)

Atomic layer deposition of silicon oxide films were conducted using thefollowing precursor: DMATMS. The depositions were performed on thelaboratory scale ALD processing tool. The silicon precursor wasdelivered to the chamber by vapor draw. Deposition process andparameters are provided in Table 4. Steps 1 to 6 are repeated until adesired thickness is reached. At 500° C., with the DMATMS precursor dosetime of 8 seconds and ozone flow for 4 seconds, the film growth rate percycle measured was 1.24 Å/cycle and film refractive index was 1.43.

Example 11: Atomic Layer Deposition of Silicon Oxide Films with1,3-Bis(Dimethylamino)-1,1,3,3-Tetramethyldisiloxane

Atomic layer deposition of silicon oxide films were conducted using thefollowing precursors:1,3-Bis(Dimethylamino)-1,1,3,3-Tetramethyldisiloxane. The depositionswere performed on the laboratory scale ALD processing tool. The siliconprecursor was delivered to the chamber by vapor draw. Deposition processand parameters are provided in Table 4. Steps 1 to 6 are repeated untila desired thickness is reached.

TABLE 4 Process for Atomic Layer Deposition of Silicon Oxide Films withOxygen Source Using DMATMS. Step 1 6 sec Evacuate reactor <100 mT Step2a variable Dose Silicon precursor Reactor pressure typically < 2 TorrStep 2b 6 sec Purge reactor with nitrogen Flow 1.5 slpm N₂ Step 2c 6 secEvacuate reactor <100 mT Step 3 variable Dose oxygen source ozone Step 46 sec Purge reactor with nitrogen Flow 1.5 slpm N₂

The process parameters of the depositions, the deposition rate andrefractive index are provided in Table 5.

TABLE 5 Summary of Process Parameters and Results for1,3-Bis(Dimethylamino)-1,1,3,3-Tetramethyldisiloxane Wafer PrecursorDeposition temperature dose Ozone dose Rate Refractive (Celcius)(seconds) (seconds) (Å/cycle) Index 300 12 + 12 10 1.58 1.46 500 12 101.53 1.54 600 12 + 12 10 1.65 1.43 650 12 10 1.66 1.45 700 12 10 2.001.45

It can be seen that precursor,1,3-Bis(Dimethylamino)-1,1,3,3-tetramethyldisiloxane with Si—O—Silinkage, provides higher growth rate per cycle compare to precursorDMATMS without the Si—O—Si linkage.

The film deposited at 650° C. and 700° C. composition were analyzed bySIMS. Film WER is done in 1:99 diluted HF solution and thermal oxidewafers were used as reference. The SIMS analysis data and relative WERis shown in Table 6. The film shows low C, H, N impurities and low WER,indicating high quality films are obtained.

TABLE 6 SIMS analysis and relative WER to thermal oxide for1,3-bis(dimethylamino)-1,1,3,3- tetramethyldisiloxane deposited at 650°C. and 700° C. Relative WER Dep T to thermal Precursor (° C.) C H Noxide 1,3- 650 2.8E+19 1.9E+21 6.9E+18 3.4 bis(dimethylamino)- 1,1,3,3-tetramethyldisiloxane 1,3- 700 1.0E+19 8.8E+20 6.6E+18 3.3bis(dimethylamino)- 1,1,3,3- tetramethyldisiloxane

Comparative Example 10a: PEALD Silicon Oxide UsingDimethylaminotrimethylsilane (DMATMS)

Depositions were done with DMATMS as Si precursor and O₂ plasma underconditions given in Table 7. DMATMS as Si precursor was delivered byvapor draw at ambient temperature (25° C.). The vessel is equipped withorifice with diameter of 0.005″ to limit precursor flow.

TABLE 7 PEALD Parameters for Silicon Oxide Using DMATMS Step A IntroduceSi wafer to the reactor Deposition temperature = 100° C. B Introduce Siprecursor to the reactor Precursor pulse = 4 seconds; Argon flow = 300sccm Reactor pressure = 3 Torr C Purge Si precursor with inert gas Argonflow = 300 sccm (argon) Argon flow time = 2 seconds Reactor pressure = 3Torr D Oxidation using plasma Argon flow = 300 sccm Oxygen flow = 100sccm Plasma power = 200 W Plasma time = 2 seconds Reactor pressure = 3Torr E Purge O₂ plasma Plasma off Argon flow = 300 sccm Argon flow time= 0.5 seconds Reactor pressure = 3 Torr

Steps b to e were repeated 500 times to get a desired thickness ofsilicon oxide for metrology. With the Si precursor pulse of 4 seconds,film growth rate measured to be around 0.8 Å/cycle for differentprecursor pulse time.

Example 12: PEALD Silicon Oxide Using1,3-Bis(Dimethylamino)-1,1,3,3-Tetramethyldisiloxane

Depositions were done with1,3-Bis(Dimethylamino)-1,1,3,3-Tetramethyldisiloxane as Si precursor andO₂ plasma under conditions given in Table 8.1,3-Bis(Dimethylamino)-1,1,3,3-Tetramethyldisiloxane as Si precursor wasdelivered by carrier gas at ambient temperature (25° C.).

TABLE 8 PEALD Parameters for Silicon Oxide Using 1,3-Bis(Dimethylamino)-1,1,3,3-Tetramethyldisiloxane Step A Introduce Siwafer to the reactor Deposition temperature = 100° or 300° C. BIntroduce Si precursor to the reactor Precursor pulse = variableseconds; Carrier gas Argon flow = 200 sccm Process gas Argon flow = 300sccm Reactor pressure = 3 Torr C Purge Si precursor with inert gas Argonflow = 300 sccm (argon) Argon flow time = 2 seconds Reactor pressure = 3Torr D Oxidation using plasma Argon flow = 300 sccm Oxygen flow = 100sccm Plasma power = 200 W Plasma time = 2 seconds Reactor pressure = 3Torr E Purge O₂ plasma Plasma off Argon flow = 300 sccm Argon flow time= 0.5 seconds Reactor pressure = 3 Torr

Steps b to e were repeated 200 times to get a desired thickness ofsilicon oxide for metrology. The film growth rate and refractive indexare shown in Table 9.

TABLE 9 Summary of PEALD Process Parameters and Results for1,3-Bis(Dimethylamino)-1,1,3,3-Tetramethyldisiloxane Wafer Precursortemperature dose Growth Rate Refractive (Celcius) (seconds) (Å/cycle)Index 100 1 1.05 1.47 100 4 1.84 1.50 100 8 1.85 1.50 300 1 1.36 1.46300 2 1.44 1.46 300 4 1.48 1.52

It can be seen that 1,3-Bis(Dimethylamino)-1,1,3,3-Tetramethyldisiloxanewith Si—O—Si linkage gives higher growth rate per cycle compared toprecursor dimethylaminotrimethylsilane without Si—O—Si linkage.

Example 13: Atomic Layer Deposition of Silicon Oxide Films with1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane

Atomic layer deposition of silicon oxide films were conducted using thefollowing precursors: 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane.The depositions were performed on the laboratory scale ALD processingtool. The silicon precursor was delivered to the chamber by vapor draw.Deposition process and parameters are provided in Table 4. Steps 1 to 6are repeated until a desired thickness is reached. The processparameters of the depositions, the deposition rate and refractive indexare provided in Table 10.

TABLE 10 Summary of Process Parameters and Results for1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane. Wafer PrecursorDeposition Relative WER temperature dose Ozone dose Rate Refractive tothermal (Celcius) (seconds) (seconds) (Å/cycle) Index oxide 300 12 101.77 1.45 9.2 400 12 10 2.16 1.44 8.3 650 12 10 1.92 1.44 3.2 650 12 201.91 1.45 3.8 700 12 10 2.10 1.44 2.8 700 12 20 2.07 1.45 3.1

The high temperature deposited (≥650° C.) films' composition analysis isshown in Table 11.

TABLE 11 SIMS composition analysis of film deposited by1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane Wafer temperature OzoneTime (Celcius) (s) C H N 700 10 2.52E+19 2.81E+20 8.38E+17 700 201.65E+19 2.29E+20 5.55E+17 650 10 2.75E+19 4.76E+20 1.35E+18 650 201.59E+19 5.81E+20 1.86E+18

It can be seen that precursor,1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane with Si—O—Si linkage,provides higher growth rate per cycle compared to precursor DMATMSwithout the Si—O—Si linkage. The film deposited at high temperature haslow C, N, H impurities and low relative WER to thermal oxide, indicatinghigh quality films were obtained.

The conformality of the film deposited at 650° C. was studied by TEM.The samples were imaged with a FEI Tecnai TF-20 FEG/TEM operated at 200kV in bright-field (BF) TEM mode, high-resolution (HR) TEM mode, andhigh-angle annular dark-field (HAADF) STEM mode. The STEM probe size was1-2 nm nominal diameter. The film surface coverage was 102% in themiddle side and 97% at the bottom, confirming excellent step coveragefor structured feature.

Example 14: PEALD Silicon Oxide Using1,5-Bis(dimethylamino)-1,1,3,3,5,5-hexamethyltrisiloxane

Depositions were done with1,5-Bis(dimethylamino)-1,1,3,3,5,5-hexamethyltrisiloxane as Si precursorand O₂ plasma under conditions given in Table 12.1,5-Bis(dimethylamino)-1,1,3,3,5,5-hexamethyltrisiloxane as Si precursorwas delivered by carrier gas at 70° C.

TABLE 12 PEALD Parameters for Silicon Oxide Using 1,5-Bis(dimethylamino)-1,1,3,3,5,5-hexamethyltrisiloxane. Step a IntroduceSi wafer to the reactor Deposition temperature = 100° or 300° C. bIntroduce Si precursor to the reactor Precursor pulse = variableseconds; Carrier gas Argon flow = 200 sccm Process gas Argon flow = 300sccm Reactor pressure = 3 Torr c Purge Si precursor with inert gas Argonflow = 300 sccm (argon) Argon flow time = 2 seconds Reactor pressure = 3Torr d Oxidation using plasma Argon flow = 300 sccm Oxygen flow = 100sccm Plasma power = 200 W Plasma time = 5 seconds Reactor pressure = 3Torr e Purge O₂ plasma Plasma off Argon flow = 300 sccm Argon flow time= 2 seconds Reactor pressure = 3 Torr

Steps b to e were repeated 200 times to get a desired thickness ofsilicon oxide for metrology. The film growth rate and refractive indexare shown in Table 13.

TABLE 13 Summary of PEALD Process Parameters and Results for1,5-Bis(dimethylamino)-1,1,3,3,5,5-hexamethyltrisiloxane. WaferPrecursor temperature dose Growth Rate Refractive (Celcius) (seconds)(Å/cycle) Index 100 8 2.37 1.45 100 16 2.40 1.44 300 8 1.93 1.46

It can be seen that1,5-Bis(dimethylamino)-1,1,3,3,5,5-hexamethyltrisiloxane with Si—O—Silinkage gives higher growth rate per cycle compare to precursordimethylaminotrimethylsilane without Si—O—Si linkage.

Although certain principles of the invention have been described abovein connection with aspects or embodiments, it is to be clearlyunderstood that this description is made only by way of example and notas a limitation of the scope of the invention.

The invention claimed is:
 1. A method of depositing a film comprisingsilicon and oxygen onto a substrate, the method comprising the steps of:a) providing a substrate in a reactor; b) introducing into the reactorat least one silicon precursor compound, wherein the at least onesilicon precursor compound is selected from the group consisting ofFormulae A and B:

 wherein R¹ is independently selected from the group consisting of alinear C₁ to C₁₀ alkyl group, a branched C₃ to C₁₀ alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ heterocyclic group, a C₃ to C₁₀alkenyl group, a C₃ to C₁₀ alkynyl group, and a C₄ to C₁₀ aryl group; R²is selected from the group consisting of hydrogen, a C₁ to C₁₀ linearalkyl group, a branched C₃ to C₁₀ alkyl group, a C₃ to C₁₀ cyclic alkylgroup, a C₃ to C₁₀ heterocyclic group, a C₃ to C₁₀ alkenyl group, a C₃to C₁₀ alkynyl group, and a C₄ to C₁₀ aryl group, wherein R¹ and R² inFormula A or B are either linked to form a cyclic ring structure or arenot linked to form a cyclic ring structure; R³⁻⁸ are each independentlyselected from the group consisting of hydrogen, a linear C₁ to C₁₀ alkylgroup, a branched C₃ to C₁₀ alkyl group, a C₃ to C₁₀ cyclic alkyl group,a C₂ to C₁₀ alkenyl group, a C₂ to C₁₀ alkynyl group, and a C₄ to C₁₀aryl group; X is selected from the group consisting of hydrogen, alinear C₁ to C₁₀ alkyl group, a branched C₃ to C₁₀ alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₂ to C₁₀ alkenyl group, a C₂ to C₁₀ alkynylgroup, and a C₄ to C₁₀ aryl group, wherein R¹ and R⁹ are either linkedto form a cyclic ring or are not linked to form a cyclic ring, andwherein both of R³ and R⁴ are not hydrogen; c) purging the reactor withpurge gas; d) introducing an oxygen-containing source into the reactor;and e) purging the reactor with purge gas, wherein steps b through e arerepeated until a desired thickness of the film is deposited, and whereinthe method is conducted at one or more temperatures ranging from about600° C. to about 800° C.
 2. The method of claim 1, wherein the at leastone silicon precursor compound is at least one selected from the groupconsisting of 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane,1-diethylamino-1,1,3,3,3-pentamethyldisiloxane,1-di-iso-propylamino-1,1,3,3,3-pentamethyldisiloxane,1-di-sec-butylamino-1,1,3,3,3-pentamethyldisiloxane,1-pyrrolyl-1,1,3,3,3-pentamethyldisiloxane,1-pyrrolidino-1,1,3,3,3-pentamethyldisiloxane,1-piperidino-1,1,3,3,3-pentamethyldisiloxane,1-(2,6-dimethylpiperidino)-3,3,3-pentamethyldisiloxane,1-dimethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane,1-diethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane,1-di-iso-propylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane,1-sec-butylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane,1-cyclohexylmethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane,1-cyclohexylethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane,1-piperidino-1,1,3,3,5,5,5-heptamethyltrisiloxane,1-(2,6-dimethylpiperidino)-1,1,3,3,5,5,5-heptamethyltrisiloxane,1-pyrrolyl-1,1,3,3,5,5,5-heptamethyltrisiloxane, and1-pyrrolidino-1,1,3,3,5,5,5-heptamethyltrisiloxane.
 3. The method ofclaim 1, wherein the oxygen-containing source is selected from the groupconsisting of an oxygen plasma, a plasma comprising oxygen and argon, aplasma comprising oxygen and helium, an ozone plasma, a water plasma, anitrous oxide plasma, a carbon dioxide plasma, a carbon monoxide plasma,and combinations thereof.
 4. The method of claim 1 wherein theoxygen-containing source comprises plasma.
 5. The method of claim 4wherein the plasma is generated in situ.
 6. The method of claim 4wherein the plasma is generated remotely.
 7. The method of claim 4wherein the film has a density of about 2.1 g/cc or greater.
 8. Themethod of claim 1 wherein the film further comprises carbon.
 9. Themethod of claim 8 wherein the film has a density of about 1.8 g/cc orgreater.
 10. The method of claim 8 wherein a carbon content of the filmis 0.5 atomic weight percent (at. %) as measured by x-rayphotospectroscopy or greater.
 11. The method of claim 1 wherein the atleast one silicon precursor compound is selected from the groupconsisting of 1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane,1-diethylamino-1,1,3,3,3-pentamethyldisiloxane, and1-pyrrolidino-1,1,3,3,3-pentamethyldisiloxane.
 12. The method of claim11 wherein the at least one silicon precursor compound is1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane.
 13. The method of claim1 wherein the at least one silicon precursor compound is substantiallyfree of halide ions.
 14. The method of claim 13 wherein the at least onesilicon precursor compound comprises less than 5 ppm of halide ions. 15.The method of claim 14 wherein the at least one silicon precursorcompound comprises less than 3 ppm of halide ions.
 16. The method ofclaim 15 wherein the at least one silicon precursor compound comprisesless than 1 ppm of halide ions.
 17. The method of claim 16 wherein theat least one silicon precursor compound is free of halide ions.
 18. Amethod of depositing a film comprising silicon and oxygen onto asubstrate comprises steps of: a) providing a substrate in a reactor; b)introducing into the reactor at least one silicon precursor compound,wherein the at least one silicon precursor compound is selected from thegroup consisting of Formulae A and B:

 wherein R¹ is independently selected from the group consisting of alinear C₁ to C₁₀ alkyl group, a branched C₃ to C₁₀ alkyl group, a C₃ toC₁₀ cyclic alkyl group, a C₃ to C₁₀ heterocyclic group, a C₃ to C₁₀alkenyl group, a C₃ to C₁₀ alkynyl group, and a C₄ to C₁₀ aryl group; R²is selected from the group consisting of hydrogen, a C₁ to C₁₀ linearalkyl group, a branched C₃ to C₁₀ alkyl group, a C₃ to C₁₀ cyclic alkylgroup, a C₃ to C₁₀ heterocyclic group, a C₃ to C₁₀ alkenyl group, a C₃to C₁₀ alkynyl group, and a C₄ to C₁₀ aryl group, wherein R¹ and R² inFormula A or B are either linked to form a cyclic ring structure or arenot linked to form a cyclic ring structure; and R³⁻⁸ and X are methyl;c) purging the reactor with purge gas; d) introducing anoxygen-containing source into the reactor; and e) purging the reactorwith purge gas, wherein steps b through e are repeated until a desiredthickness of the film is deposited, and wherein the method is conductedat one or more temperatures ranging from about 600° C. to about 800° C.19. The method of claim 18, wherein the at least one silicon precursorcompound is at least one selected from the group consisting of1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane,1-diethylamino-1,1,3,3,3-pentamethyldisiloxane,1-di-iso-propylamino-1,1,3,3,3-pentamethyldisiloxane,1-di-sec-butylamino-1,1,3,3,3-pentamethyldisiloxane,1-pyrrolyl-1,1,3,3,3-pentamethyldisiloxane,1-pyrrolidino-1,1,3,3,3-pentamethyldisiloxane,1-piperidino-1,1,3,3,3-pentamethyldisiloxane,1-(2,6-dimethylpiperidino)-3,3,3-pentamethyldisiloxane,1-dimethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane,1-diethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane,1-di-iso-propylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane,1-sec-butylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane,1-cyclohexylmethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane,1-cyclohexylethylamino-1,1,3,3,5,5,5-heptamethyltrisiloxane,1-piperidino-1,1,3,3,5,5,5-heptamethyltrisiloxane,1-(2,6-dimethylpiperidino)-1,1,3,3,5,5,5-heptamethyltrisiloxane,1-pyrrolyl-1,1,3,3,5,5,5-heptamethyltrisiloxane, and1-pyrrolidino-1,1,3,3,5,5,5-heptamethyltrisiloxane.
 20. The method ofclaim 18, wherein the at least one silicon precursor compound is atleast one selected from the group consisting of1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane,1-diethylamino-1,1,3,3,3-pentamethyldisiloxane, and1-pyrrolidino-1,1,3,3,3-pentamethyldisiloxane.
 21. The method of claim20 wherein the at least one silicon precursor compound is1-dimethylamino-1,1,3,3,3-pentamethyldisiloxane.
 22. The method of claim18 wherein the at least one silicon precursor compound is substantiallyfree of halide ions.
 23. The method of claim 22 wherein the at least onesilicon precursor compound comprises less than 5 ppm of halide ions. 24.The method of claim 23 wherein the at least one silicon precursorcompound comprises less than 3 ppm of halide ions.
 25. The method ofclaim 24 wherein the at least one silicon precursor compound comprisesless than 1 ppm of halide ions.
 26. The method of claim 25 wherein theat least one silicon precursor compound is free of halide ions.